EP1276785B1 - Polyurethane coatings, based on polyisocyanates containing uretdione and/or oxadiazinetrione groups - Google Patents
Polyurethane coatings, based on polyisocyanates containing uretdione and/or oxadiazinetrione groups Download PDFInfo
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- EP1276785B1 EP1276785B1 EP01955100A EP01955100A EP1276785B1 EP 1276785 B1 EP1276785 B1 EP 1276785B1 EP 01955100 A EP01955100 A EP 01955100A EP 01955100 A EP01955100 A EP 01955100A EP 1276785 B1 EP1276785 B1 EP 1276785B1
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- polyurethane coatings
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
- D06N3/147—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes characterised by the isocyanates used
- D06N3/148—(cyclo)aliphatic polyisocyanates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/798—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing urethdione groups
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C11/00—Surface finishing of leather
- C14C11/003—Surface finishing of leather using macromolecular compounds
- C14C11/006—Surface finishing of leather using macromolecular compounds using polymeric products of isocyanates (or isothiocyanates) with compounds having active hydrogen
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
- D06N3/146—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes characterised by the macromolecular diols used
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31558—Next to animal skin or membrane
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31591—Next to cellulosic
Definitions
- the invention relates to polyurethane coatings, e.g. can be prepared by the casting or doctor blade method on flexible substrates such as textile or leather by means of reactive compositions (reactive binder) based on isocyanate-containing compounds and polyols.
- reactive binder reactive binder
- Solvent-free or low-reactive reactive compositions based on NCO prepolymers for the production of polyurethane coatings on flexible substrates are known.
- EP-A 0 490 158 describes a process for the production of polyurethane coatings which is characterized by a high reactivity. Due to its high reactivity, such a process is only suitable for spray applications and, because of its very short pot life, can not be used in the casting or doctoring process.
- systems based on blocking polyisocyanates are suitable for such coating processes, e.g. the combination of blocked NCO prepolymers and cycloaliphatic diamines.
- a ketoxime-blocked NCO prepolymer based on aromatic polyisocyanates is mixed with a diamine as a chain extender and then cured by a heat treatment with elimination of the ketoxime and optionally evaporation of the solvent.
- Reactive compositions of this type for the coating of flexible substrates are e.g. described in DE-A 2 902 090. In the curing of the described systems, therefore, a cleavage of the ketoxime, which even then makes an exhaust air treatment necessary, if the systems do not contain solvents.
- EP-A 0 825 209 describes splitting-free reactive binders which, due to their favorable reaction kinetics and the very good mechanical film properties, are outstandingly suitable for coating textiles and other sheetlike substrates.
- the disadvantage here is that the production of low-monomer reactive binders requires increased technical complexity (removal of monomers by thin-film distillation).
- average molecular weights are understood to mean number average molecular weights.
- Preferred NCO prepolymers A) have average molecular weights of 1200 to 10,000, preferably of 1500 to 8000.
- the free NCO content is preferably between 1.5 and 7 wt .-%, more preferably between 2.0 and 5.0 %.
- the content of monomeric diisocyanate (diisocyanates which have no further heteroatoms) is preferably less than 0.5%.
- Preferred NCO prepolymers A) have an average NCO functionality of from 2.0 to 3.0, preferably from 2.1 to 2.8.
- the NCO prepolymers A) can be prepared by reacting uretdione- and / or oxadiazinetrione-containing organic polyisocyanates a) and optionally further polyisocyanates b) with NCO-reactive compounds c).
- the industrially available aliphatic uretdione groups-containing polyisocyanates a) are usually mixtures which may contain both isocyanurate, iminooxadiazinedione, allophanate or biuret structures.
- An example of such a product is Desmodur® N 3400 (Bayer AG, DE), a polyisocyanate based on hexamethylene diisocyanate which, in addition to uretdione groups, mainly contains isocyanurate groups and thus has an average NCO functionality of about 2.5.
- Preference is given to using uretdione-containing polyisocyanates based on hexamethylene diisocyanate.
- Oxadiazinetrione group-containing polyisocyanates are described, for example, in DE-A 1 670 666 and EP-A 0 081 712. Preference is given to 3,5-bis- [6-isocyanatohexyl] -1,3,5-oxadiazine-2,4,6-trione which is formed by addition of one mole of carbon dioxide and 2 moles of hexamethylene diisocyanate and according to DE-A 1 670 666 can be produced.
- organic polyisocyanates b) include aliphatic, cycloaliphatic and aromatic polyisocyanates.
- Suitable polyisocyanates b) are, for example, compounds of the formula Q (NCO) n having an average molecular weight below 800, where n is a number from 2 to 4 and Q is an aliphatic C 4 -C 12 -hydrocarbon radical or a cycloaliphatic C 6 -C 15 -hydrocarbon radical
- diisocyanates from the series 4,4'-diisocyanatodicyclohexylmethane, 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate (Isophorone diisocyanate IPDI), tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), 2-methylpentamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate (THDI), dodecamethylene diis
- polyisocyanates as described, for example, in "Methods of Organic Chemistry” (Houben-Weyl), Vol. 14/2, Georg Thieme Verlag, Stuttgart 1963, pages 61 to 70 and in Liebigs Annalen der Chemie 562, pages 75 to 136 may be used.
- aromatic polyisocyanates such as 2,4- and 2,6-toluene diisocyanate, their technical mixtures, or 2,4'- and 4,4'-diphenylmethane diisocyanates can be used, but are less preferred.
- Preferred NCO-reactive compounds c) are especially polyols.
- As polyols it is possible to use relatively high molecular weight and, to a lesser extent, low molecular weight hydroxyl compounds.
- Higher molecular weight hydroxyl compounds include the usual in polyurethane chemistry hydroxypolyesters, hydroxypolyethers, hydroxypolythioethers, hydroxypolyacetals, hydroxypolycarbonates, dimer fatty alcohols and / or ester amides, each having average molecular weights from 400 to 8,000, preferably those having average molecular weights from 500 to 6 500. It is preferably only diols are used since the branching is usually introduced via the polyisocyanate component a) or b).
- polystyrene resin As low molecular weight polyhydroxyl compounds in polyurethane chemistry conventional polyols, with molecular weights of 62 to 399, such as ethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol and 1,3, 1,4-butanediol and 1,3, hexanediol 1,6, octanediol-1,8, neopentyl glycol, 1,4-bis (hydroxymethyl) cyclohexane, bis (hydroxymethyl) tricyclo [5.2.1.0 2.6] decane or 1,4-bis (2-hydroxyethoxy) benzene, 2- Methyl-1,3-propanediol, 2,2,4-trimethylpentanediol, 2-ethyl-1,3-hexanediol, dipropylene glycol, polypropylene glycols, dibutylene glycol, polybutylene glycols, bis
- Suitable polyether polyols are the polyethers customary in polyurethane chemistry, e.g. the addition or Mischadditionseducationen of tetrahydrofuran, styrene oxide, ethylene oxide, propylene oxide, the butylene oxides or epichlorohydrin, in particular of the prepared using two- to hexavalent starter molecules such as water or the above-mentioned polyols or 1- to 4-NH bonds Ethylene oxide and / or propylene oxide.
- Suitable polyester polyols are e.g. Reaction products of polyhydric, preferably dihydric and optionally additionally trihydric alcohols with polybasic, preferably dibasic carboxylic acids.
- polyhydric preferably dihydric and optionally additionally trihydric alcohols
- polybasic preferably dibasic carboxylic acids.
- free polycarboxylic acids it is also possible to use the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols or mixtures thereof to prepare the polyesters.
- the polycarboxylic acids may be aliphatic, cycloaliphatic, aromatic and / or heterocyclic in nature, and optionally, e.g. substituted by halogen atoms and / or unsaturated. Examples for this are:
- Adipic phthalic, isophthalic, succinic, suberic, azelaic, sebacic, trimellitic, phthalic, tetrahydrophthalic, glutaric, tetrachlorophthalic, endomethylenetetrahydrophthalic anhydride, Maleic anhydride, maleic acid, fumaric acid, dimeric and trimeric fatty acids such as oleic acid, optionally in admixture with monomeric fatty acids, terephthalic acid dimethyl ester, terephthalic acid bis-glycol ester.
- Suitable polyhydric alcohols are the abovementioned polyols.
- the polycarbonate polyols in question are obtainable by reaction of carbonic acid derivatives, for example diphenyl carbonate or phosgene, with diols.
- diols are ethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol and 1,3-butanediol-1,4-and 1,3-pentanediol-1,5-hexanediol-1,6-octanediol-1 , 8, Neopentylgkylol, 1,4-bis (hydroxymethyl) cyclohexane, bis (hydroxymethyl) tricyclo [5.2.1.0 2.6] decane or 1,4-bis (2-hydroxyethoxy) benzene, 2-methyl-1,3-propanediol , 2,2,4-trimethylpentanediol, dipropylene glycol, polypropylene glycols, dibutylene glycol, polybutylene glycols
- the diol component contains 40 to 100 wt .-% of hexanediol, preferably 1,6-hexanediol, and / or hexanediol derivatives, preferably those which in addition to terminal OH groups ether or ester groups, for example products which by reaction of 1 Mol hexanediol with at least 1 mole, preferably 1 to 2 moles of caprolactone according to DE-A 1 770 245, or by etherification of hexanediol with itself to di- or Trihexylenglykol were obtained.
- the preparation of such derivatives is known, for example, from DE-A 1 570 540.
- the polyether-polycarbonate diols described in DE-A 3 717 060 can also be used.
- the hydroxypolycarbonates should be substantially linear. However, they can also be easily branched if appropriate by the incorporation of polyfunctional components, in particular low molecular weight polyols. Trimethylolpropane, hexanetriol-1,2,6, glycerol, butanetriol-1,2,4, pentaerythritol, quinitol, mannitol, sorbitol, methylglycoside and 4,3,6-dianhydrohexite are suitable for this purpose, for example.
- polyether polyols having a low degree of unsaturation which are particularly preferably usable according to the invention are known in principle and are described by way of example in DE-A 1 984 817 (PCT / 99/07883) and the publications cited therein. Key to the preparation of such low unsaturation polyether polyols is catalysis with metal cyanides.
- the preparation of component A) is preferably carried out by reacting the uretdione and / or oxadiazinetrione-containing polyisocyanate a) with said polyhydroxyl c) at about 40 to 100 ° C, wherein an NCO / OH ratio of 1.5: 1 to 5: 1, preferably 1.7: 1 to 4: 1, is set.
- Component A) can, for the purpose of setting the optimum processing viscosity of from 20,000 to 40,000 mPas at 20 ° C with up to 30 wt .-%, preferably up to 20 wt .-%, based on the NCO prepolymer, of organic solvents such as Methoxypropylacetat or butyl acetate are mixed.
- Component B) is preferably more than 80 equivalent%, more preferably 100 equivalent%, based on the isocyanate-reactive groups, of compounds of formula III.
- Preferred compounds III are compounds which do not dissolve in prepolymer A below 50 ° C.
- Particularly preferred compounds III include, for example, 1,2-bis (2-hydroxyethoxy) benzene, 1-3-bis (2-hydroxyethoxy) benzene, Bis-1,4- (hydroxymethyl) benzene, trans-1,4-bis (hydroxymethyl) cyclohexane, 1,2-bis (4-hydroxycyclohexyl) ethane, bis (4-hydroxycyclohexyl) methane, 2-butyne-1, 4-diol, The most preferred compound III is 1,4-bis (2-hydroxyethoxy) benzene.
- Component B) can be mixed as such to prepare the reactive binder directly with the prepolymer. However, it has proved to be favorable for better dosing to touch the normally solid compounds III in a liquid component. Such mixtures then preferably consist of 20 to 90, more preferably 30 to 70 wt.% Compounds III and 10 to 80, particularly preferably 30 to 70 wt .-% liquid component and 0 to 10 wt%, preferably 0.1 to 5 % By weight of further additives such as dispersants, anti-settling agents, catalysts, etc.
- the liquid component may be one of the above-described higher molecular weight polyols and / or a non-isocyanate-reactive plasticizer and / or any desired solvent.
- suitable solvents are the conventional lacquer solvents: esters such as butyl acetate, ether esters such as methoxypropyl acetate, ketones such as acetone and 2-butanone, aromatics such as xylene, toluene or technical aromatic or aliphatic mixtures or else dipolar solvents such as N-methylpyrrolidone, N, N- Dimethylacetamide, N, N-dimethylformamide and dimethyl sulfoxide or mixtures of various solvents.
- esters such as butyl acetate
- ether esters such as methoxypropyl acetate
- ketones such as acetone and 2-butanone
- aromatics such as xylene, toluene or technical aromatic or aliphatic mixtures
- dipolar solvents such as N-methylpyrrolidone, N, N- Dimethylacetamide, N, N-dimethylformamide and dimethyl sulfoxide or mixtures of various solvents.
- solvents are preferred. Particularly preferred are less toxic aliphatic esters or ether esters such as methoxypropyl acetate or butyl acetate.
- the solid compound III is in fine distribution.
- the compound III is then usually incorporated with a dissolver in the liquid component. But it is also possible, a supersaturated solution of compound III by recrystallization into the desired dispersion or to disperse the compound III from the melt. A production in the usual in the paint industry bead mills is also possible.
- the rheological properties and the settling behavior can be favorably influenced by special additives such as hydrogenated castor oils, polyurea derivatives or special silicic acids (see J. Beilman, "Lackadditive”, Wiley-VCH-Verlag GmbH, 1998).
- dispersants in particular polymeric additives are suitable. They preferably consist of chemically different segments which, depending on the structure, either interact with the surface of the particles to be dispersed or, as solvated chains, contribute to their steric stabilization.
- the functional groups which may interact with the pigment or filler particles or with the crystalline compound III in the crosslinker component B according to the invention are carbonyl, amino, sulfate or phosphate groups.
- polymer segments which contribute to the stabilization of the particles are polyethers, polyesters or polyacrylates.
- the amount of catalysts according to the invention which can be used as constituent of component B or as catalyst solution in any solvent is 0.001 to 2, preferably 0.005 to 0.5,% by weight, based on the total weight of component A + component B.
- Ganz Particularly suitable for the purposes of the invention are dioctyltin-IV-bis (2-ethylhexylmercaptoacetate), dibutyltin-IV-bis (2-ethylhexylmercaptoacetate) and dimethyltin-IV-bis (2-ethylhexylmercaptoacetate) and also latent catalysts of tin or bismuth compounds and mercapto compounds, as they eg in US Pat. No. 4,788,083.
- the mixing of the NCO prepolymer A with the chain extender component B is generally about in the ratio of the equivalent weights of these components, although for some applications, a sub-crosslinking is appropriate, so that the equivalent ratio of NCO to OH according to the invention generally 0.90 to 1.50 , preferably 1.0 to 1.3.
- additives such as e.g. Pigments, UV stabilizers, flow control agents, antioxidants, fillers or blowing agents.
- Paint assistants can be used, as described, for example, in J. Beilman, "Lackadditive”, Wiley-VCH-Verlag GmbH, 1998.
- flow and dispersants and rheological additives are suitable for the preparation of the compositions of the invention.
- silicone-based additives can be used to improve surface properties.
- suitable additives based on polyacrylates are particularly suitable additives based on polyacrylates.
- the rheological properties of the compositions and the settling behavior of fillers and pigment-containing compositions can be favorably influenced by special additives such as hydrogenated castor oils, polyurea derivatives or special silicas.
- Lacquer additives which can be added to the compositions of the invention can be used in amounts of from 0.01 to 5% by weight, preferably from 0.05 to 3% by weight.
- flame-retardant additives can be added to the compositions of the invention.
- These are solid or liquid substances whose addition causes an improvement in the fire behavior of the cured polymer film. These agents are described, for example, in Journal of Coated Fabrics 1996, Vol. 25, 224 et seq.
- Particularly suitable for use in the compositions of the invention are halogen and Antimonfieie flame retardants such as phosphoric or boric acid derivatives, calcium carbonate, aluminum hydroxide, magnesium hydroxide or melamine and melamine derivatives.
- Particularly preferred is melamine and its derivatives such as melamine borate or melamine isocyanurate.
- the flame retardants may be added to the compositions of the invention to 2 to 70 wt .-%, preferably 5 to 35 wt .-%, based on the sum of the component A + B.
- the reactive compositions according to the invention are preferably processed by doctoring (brushing) by the direct or reverse coating method.
- the curing time of the compositions according to the invention is 2 to 18, preferably 6 to 12 minutes.
- the short curing time makes it possible to coat at high speed.
- the preparation of, for example, a reverse coating may for example be done as follows: It is first applied to a suitable intermediate support, eg a release paper, the reactive composition for the top coat in an amount of about 30 to 100 g / m 2, cured in a drying tunnel, brings to the dry top coat, the reactive composition for the adhesive coat also in an amount of about 30 to 100 g / m 2, laminated thereto, the substrate, the coating is cured in another drying tunnel at about 120 to 190 ° C, preferably 140 to 170 ° C, and withdraws the coated substrate from the release liner.
- a suitable intermediate support eg a release paper
- the reactive composition for the top coat in an amount of about 30 to 100 g / m 2, cured in a drying tunnel
- the coating is cured in another drying tunnel at about 120 to 190 ° C, preferably 140 to 170 ° C, and withdraws the coated substrate from the release liner.
- the reactive compositions can also be applied directly to the textile substrate in a direct coating process.
- the splitter-free and low-solvent character of the reactive compositions of the invention is of great advantage in the production of thick tarpaulin coatings. With application quantities of 100 to 200 g / m 2 , about 0.4 mm thick, technical coatings can be created in this way in only one operation.
- foam layers are to be produced with the reactive compositions according to the invention, then they are added to blowing agents and, expediently, to foam stabilizers.
- Suitable additives are described, for example, in DE-A 1 794 006 and in US Pat. No. 3,262,805.
- Desmophen® C200 linear polyester carbonate diol of average molecular weight 2,000, Bayer AG, DE
- Desmophen® C200 linear polyester carbonate diol of average molecular weight 2,000, Bayer AG, DE
- isophorone diisocyanate 150 g
- methoxypropyl acetate a further 571 g of methoxypropyl acetate are added and cooled to 40 ° C.
- 772 g (4 equiv) of Desmodur® N 3400 (Bayer AG, DE) are added in one pour and heated to 75 ° C. until an NCO content of 3.1% is reached.
- the prepolymer has a solids content of 80% and an isocyanate equivalent weight of 1 355 g.
- 2,000 g (2 equiv.) Of polytetrahydrofuran having an average molecular weight of 2,000 (Terathane® 2000, DuPont) is initially mixed at 100 ° C. with 111 g (1 equiv) of isophorone diisocyanate until the disappearance of the isocyanate band in the IR spectrum implemented. Subsequently, 683 g of methoxypropyl acetate are added and cooled to 40 ° C. 579 g (3 equiv.) Desmodur.RTM. N 3400 (Bayer AG, DE) are added in one pour and the mixture is heated to 75.degree. C. until an NCO content of 2.4% is reached.
- the prepolymer has a solids content of 80% and an isocyanate equivalent weight of 1 750 g.
- 100 g of the prepolymer A1 are mixed with 14.2 g of component B, 1 g of the leveling agent Levacast® Fluid SN (Bayer AG, DE) and 0.5 g of Irganox® 1010 (Ciba Specialties).
- the mixture has an initial viscosity of about 29,000 mPas, measured at 23 ° C.
- the mixture is cured by stepwise heat treatment (3 min. 120 ° C and 3 min 150 ° C).
- An elastic, homogeneous film with the following mechanical properties is obtained: Module (100%) 3.3 MPa tensile strength 10.9 MPa elongation 470% Essigesterquellung 187% melting range 222-226 ° C
- 100 g of the prepolymer A2 are mixed with 18.3 g of component B, 1 g of the leveling agent Levacast® Fluid SN (Bayer AG, DE) and 0.5 g of Irganox® 1010 (Ciba Specialties).
- the mixture has an initial viscosity of about 40,000 mPas, measured at 23 ° C.
- the mixture is cured by stepwise heat treatment (3 min. 120 ° C and 3 min 150 ° C).
- An elastic, homogeneous film with the following mechanical properties is obtained: Module (100%) 4.7 MPa tensile strength 5.8 MPa elongation 180% Essigesterquellung 140% melting range 214 ° C
- 100 g of the prepolymer A 1 are mixed with 14.2 g of component B, 1 g of the leveling agent Levacast® Fluid SN (Bayer AG, DE) and 0.5 g of Irganox® 1010 (Ciba Specialties).
- the mixture has an initial viscosity of about 45,000 mPas, measured at 23 ° C.
- the mixture is cured by stepwise heat treatment (3 min. 120 ° C and 3 min. 150 ° C).
- An elastic, homogeneous film with the following mechanical properties is obtained: Module (100%) 3.3 MPa tensile strength 4.6 MPa elongation 210% Essigesterquellung 140% melting range 220 ° C
Abstract
Description
Die Erfindung betrifft Polyurethan-Beschichtungen, die z.B. nach dem Gieß- oder Rakelverfahren auf flexiblen Substraten wie Textil oder Leder mittels reaktionsfähiger Massen (Reaktivbindemittel) auf Basis von Isocyanat-haltigen Verbindungen und Polyolen hergestellt werden können.The invention relates to polyurethane coatings, e.g. can be prepared by the casting or doctor blade method on flexible substrates such as textile or leather by means of reactive compositions (reactive binder) based on isocyanate-containing compounds and polyols.
Lösungsmittelfreie bzw. -arme reaktionsfähige Massen auf Basis von NCO-Prepolymeren zur Herstellung von Polyurethanbeschichtungen auf flexiblen Substraten sind bekannt. Beispielsweise wird in der EP-A 0 490 158 ein Verfahren zur Herstellung von Polyurethan-Beschichtungen beschrieben, das durch eine hohe Reaktivität gekennzeichnet ist. Ein solches Verfahren ist aufgrund seine hohen Reaktivität nur für Sprüh-Anwendungen geeignet und kann wegen seiner sehr geringen Topfzeit nicht im Gieß- oder Rakelverfahren eingesetzt werden. Dagegen eignen sich Systeme auf Basis von blockieren Polyisocyanaten für solche Beschichtungsverfahren, wie z.B. die Kombination aus blockierten NCO-Prepolymeren und cycloaliphatischen Diaminen. Hierbei wird ein Ketoxim-blockiertes NCO-Prepolymerisat auf Basis von aromatischen Polyisocyanaten mit einem Diamin als Kettenverlängerer gemischt und anschließend durch eine Hitzebehandlung unter Abspaltung des Ketoxims und gegebenenfalls Verdampfen des Lösungsmittels ausgehärtet. Reaktionsfähige Massen dieser Art für die Beschichtung flexibler Substrate werden z.B. in der DE-A 2 902 090 beschrieben. Bei der Härtung der beschriebenen Systeme erfolgt also eine Abspaltung des Ketoxims, die selbst dann eine Abluftbehandlung notwendig macht, wenn die Systeme keine Lösungsmittel enthalten.Solvent-free or low-reactive reactive compositions based on NCO prepolymers for the production of polyurethane coatings on flexible substrates are known. For example, EP-A 0 490 158 describes a process for the production of polyurethane coatings which is characterized by a high reactivity. Due to its high reactivity, such a process is only suitable for spray applications and, because of its very short pot life, can not be used in the casting or doctoring process. On the other hand, systems based on blocking polyisocyanates are suitable for such coating processes, e.g. the combination of blocked NCO prepolymers and cycloaliphatic diamines. Here, a ketoxime-blocked NCO prepolymer based on aromatic polyisocyanates is mixed with a diamine as a chain extender and then cured by a heat treatment with elimination of the ketoxime and optionally evaporation of the solvent. Reactive compositions of this type for the coating of flexible substrates are e.g. described in DE-A 2 902 090. In the curing of the described systems, therefore, a cleavage of the ketoxime, which even then makes an exhaust air treatment necessary, if the systems do not contain solvents.
Dagegen werden in der EP-A 0 825 209 abspalterfreie Reaktivbindemittel beschrieben, die sich aufgrund ihrer günstigen Reaktionskinetik und der sehr guten mechanischen Film-Eigenschaften hervorragend zur Beschichtung von Textilien und anderen flächigen Substraten eignen. Nachteilig ist dabei, dass die Herstellung von monomerenarmen Reaktivbindemitteln einen erhöhten technischen Aufwand (Monomerenabtrennung durch Dünnschichtdestillation) erfordert.In contrast, EP-A 0 825 209 describes splitting-free reactive binders which, due to their favorable reaction kinetics and the very good mechanical film properties, are outstandingly suitable for coating textiles and other sheetlike substrates. The disadvantage here is that the production of low-monomer reactive binders requires increased technical complexity (removal of monomers by thin-film distillation).
Der vorliegenden Erfindung lag daher die Aufgabe zugrunde, Polyurethanbeschichtungen zur Verfügung zu stellen, die aus monomerenarmen Reaktivbindemitteln erhältlich sind, welche ohne Monomerenabtrennung herstellbar sind.It is an object of the present invention to provide polyurethane coatings which are obtainable from monomer-poor reactive binders which can be prepared without monomer removal.
Überraschenderweise können durch die Kombination von bestimmter Uretdion- oder Oxadiazintriongruppen enthaltender Polyisocyanate-Prepolymere und bestimmter Diol-Kettenverlängerer Beschichtungen mit guten mechanischen Eigenschaften erhalten werden, die die Anforderungen für die Beschichtungen von flexiblen Substraten wie beispielsweise Textil erfüllen und daher diese Aufgabe lösen.Surprisingly, by combining certain polyisocyanate prepolymers containing certain uretdione or oxadiazinetrione groups and certain diol chain extenders, it is possible to obtain coatings having good mechanical properties which meet the requirements for the coatings of flexible substrates such as textiles and therefore achieve this object.
Gegenstand der Erfindung sind daher Polyurethanbeschichtungen, die dadurch gekennzeichnet sind, dass sie durch Umsetzung aliphatischer isocyanathaltige Prepolymere A) mit einer Polyolkomponente B) erhältlich sind, wobei
die Prepolymere A)
bezogen auf den Festkörper 1 bis 8 Gew.-% NCO enthalten, einen Gehalt an freiem monomeren Diisocyanat von weniger als 2 % aufweisen und einen Gehalt von 0,1 bis 1,5 mol aliphatisch angebundener Uretdion- (I) und/oder Oxadiazintriongruppen (II) pro 1000 g Prepolymer enthalten
aus mindestens 50 Äquivalent-%, bezogen auf die gegenüber Isocyanat reaktiven Gruppen, aus Verbindungen der Formel
HO-X-Y-X-OH (III)
worin
- Y
- Methylen, Ethylen, -C≡C-, Cyclohexylen,-1,4, -1,3, -1,2, Phenylen-1,4, -1,3, -1,2 und
- X
- Methylen, -OCH2CH2- (wobei der Sauerstoff an das Y gebunden ist), Cyclohexylen-1,4, -1,3, -1,2
wobei das Äquivalentverhältnis der freien NCO-Gruppen aus A zu den NCOreaktiven Gruppen von B 0,90 bis 1,50 beträgt, gegebenenfalls unter Mitverwendung üblicher Hilfsstoffe und Additive, deren Verwendung zur Beschichtung von flexiblen Substraten wie Textil oder Leder sowie Verfahren zur Beschichtung dieser Substrate, z.B. durch Gießen oder Rakeln und anschließende Hitzebehandlung sowie die beschichteten Substrate selbst.The invention therefore polyurethane coatings, which are characterized in that they are obtainable by reacting aliphatic isocyanate prepolymers A) with a polyol component B), wherein
the prepolymers A)
containing 1 to 8 wt .-% NCO based on the solid, having a content of free monomeric diisocyanate of less than 2% and a content of 0.1 to 1.5 moles of aliphatically attached uretdione (I) and / or oxadiazinetrione groups ( II) per 1000 g of prepolymer
from at least 50 equivalent%, based on the isocyanate-reactive groups, of compounds of the formula
HO-XYX-OH (III)
wherein
- Y
- Methylene, ethylene, -C≡C-, cyclohexylene, -1,4, -1,3, -1,2, phenylene-1,4, -1,3, -1,2 and
- X
- Methylene, -OCH 2 CH 2 - (where the oxygen is attached to the Y), cyclohexylene-1,4, -1,3, -1,2
wherein the equivalent ratio of the free NCO groups of A to the NCO-reactive groups of B is 0.90 to 1.50, optionally with the concomitant use of conventional auxiliaries and additives, their use for coating flexible substrates such as textile or leather, and processes for coating these substrates For example, by casting or knife coating and subsequent heat treatment and the coated substrates themselves.
Im Nachfolgenden werden unter "mittleren Molekulargewichten" jeweils als Zahlenmittel bestimmten Molekulargewichte verstanden.Hereinafter, "average molecular weights" are understood to mean number average molecular weights.
Bevorzugte NCO-Prepolymere A) besitzen mittlere Molekulargewichte von 1200 bis 10 000, vorzugsweise von 1500 bis 8 000. Der freie NCO-Gehalt liegt vorzugsweise zwischen 1,5 und 7 Gew.-%, besonders bevorzugt zwischen 2,0 und 5,0 %. Der Gehalt an monomerem Diisocyanat (Diisocyanate, die keine weiteren Heteroatome aufweisen) liegt vorzugsweise unter 0,5 %. Bevorzugte NCO-Prepolymere A) weisen eine mittlere NCO-Funtionalität von 2,0 bis 3,0, bevorzugt 2,1 bis 2,8 auf.Preferred NCO prepolymers A) have average molecular weights of 1200 to 10,000, preferably of 1500 to 8000. The free NCO content is preferably between 1.5 and 7 wt .-%, more preferably between 2.0 and 5.0 %. The content of monomeric diisocyanate (diisocyanates which have no further heteroatoms) is preferably less than 0.5%. Preferred NCO prepolymers A) have an average NCO functionality of from 2.0 to 3.0, preferably from 2.1 to 2.8.
Die NCO-Prepolymeren A) können durch Umsetzung von Uretdion- und/oder Oxadiazintrion-Gruppen enthaltenden organischen Polyisocyanaten a) und gegebenfalls weiteren Polyisocyanaten b) mit gegenüber NCO reaktiven Verbindungen c) hergestellt werden.The NCO prepolymers A) can be prepared by reacting uretdione- and / or oxadiazinetrione-containing organic polyisocyanates a) and optionally further polyisocyanates b) with NCO-reactive compounds c).
Bei den technisch verfügbaren aliphatischen Uretdion-Gruppen enthaltenden Polyisocyanaten a) handelt es sich üblicherweise um Gemische, die sowohl Isocyanurat-, Iminooxadiazindion-, Allophanat oder Biuretstrukturen enthalten können. Ein Beispiel für ein solches Produkt ist Desmodur® N 3400 (Bayer AG, DE), ein Polyisocyanat auf Basis Hexamethylendiisocyanat, das neben Uretdiongruppen vor allem Isocyanuratgruppen enthält und somit eine mittlere NCO-Funktionalität von ca. 2,5 aufweist. Vorzugsweise werden Uretdiongruppen enthaltende Polyisocyanate auf Basis Hexamethylendiisocyanat eingesetzt.The industrially available aliphatic uretdione groups-containing polyisocyanates a) are usually mixtures which may contain both isocyanurate, iminooxadiazinedione, allophanate or biuret structures. An example of such a product is Desmodur® N 3400 (Bayer AG, DE), a polyisocyanate based on hexamethylene diisocyanate which, in addition to uretdione groups, mainly contains isocyanurate groups and thus has an average NCO functionality of about 2.5. Preference is given to using uretdione-containing polyisocyanates based on hexamethylene diisocyanate.
Oxadiazintrion-Gruppen enthaltende Polyisocyanate sind beispielweise in der DE-A 1 670 666 und EP-A 0 081 712 beschrieben. Bevorzugt ist 3,5-Bis-[6-isocyanato-hexyl]-1,3,5-oxadiazin-2,4,6-trion, das durch Addition von einem Mol Kohlendioxid und 2 Mol Hexamethylendiisocyanat gebildet wird und gemäß DE-A 1 670 666 hergestellt werden kann.Oxadiazinetrione group-containing polyisocyanates are described, for example, in DE-A 1 670 666 and EP-A 0 081 712. Preference is given to 3,5-bis- [6-isocyanatohexyl] -1,3,5-oxadiazine-2,4,6-trione which is formed by addition of one mole of carbon dioxide and 2 moles of hexamethylene diisocyanate and according to DE-A 1 670 666 can be produced.
Vorzugsweise werden Uretdion-Gruppen enthaltende Polyisocyanate und Oxadiazintrion-Gruppen enthaltende Polyisocyanate in Mischung eingesetzt, wobei das Molverhältnis Oxadiazintrion-Gruppen zu Uretdion-Gruppen vorzugsweise 1,0 bis 5,0, besonders bevorzugt 2,0 bis 4,0 beträgt.Preference is given to using polyisocyanates containing uretdione groups and polyisocyanates containing oxadiazinetrione groups in mixture, the molar ratio of oxadiazinetrione groups to uretdione groups preferably being 1.0 to 5.0, particularly preferably 2.0 to 4.0.
Als weitere organische Polyisocyanate b) kommen aliphatische, cycloaliphatische und aromatische Polyisocyanate in Betracht. Geeignete Polyisocyanate b) sind beispielsweise Verbindungen der Formel Q(NCO)n mit einem mittleren Molekulargewicht unter 800, worin n eine Zahl von 2 bis 4 und Q einen aliphatischen C4-C12-Kohlenwasserstoffrest oder einen cycloaliphatischen C6-C15-Kohlenwasserstoffrest bedeuten, beispielsweise Diisocyanate aus der Reihe 4,4'-Diisocyanatodicyclohexylmethan, 3-Isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanat (Isophorondiisocyanat = IPDI), Tetramethylendiisocyanat, Hexamethylendiisocyanat (HDI), 2-Methyl-pentamethylendiisocyanat, 2,2,4-Trimethylhexamethylendiisocyanat (THDI), Dodecamethylendiisocyanat, 1,4-Diisocyanatocyclohexan, 4,4'-Diisocyanato-3,3'-dimethyl-dicyclohexylmethan, 4,4'-Diisocyanatodicyclohexylpropan-(2,2), 3-Isocyanatomethyl-1-methyl-1-isocyanatocyclohexan (IMCI), 1,3-Diisooctylcyanato-4-methyl-cyclohexan, 1,3-Diisocyanato-2-methyl-cyclohexan und α,α,α',α'-Tetramethyl-m- oder -p-xylylen-diisocyanat (TMXDI) sowie aus diesen Verbindungen bestehende Gemische. Des weiteren können Polyisocyanate, wie sie z.B. in "Methoden der organischen Chemie" (Houben-Weyl), Bd. 14/2, Georg Thieme-Verlag, Stuttgart 1963, Seiten 61 bis 70 und in Liebigs Annalen der Chemie 562, Seiten 75 bis 136 beschrieben sind, mitverwendet werden. Auch aromatische Polyisocyanate wie 2,4- und 2,6-Toluylendiisocyanat, deren technische Gemische, oder 2,4'- und 4,4'-Diphenylmethandiisocyanate können mitverwendet werden, sind aber weniger bevorzugt. Besonders bevorzugt ist jedoch die Verwendung von aliphatischen Diisocyanaten und ganz besonders bevorzugt ist die Verwendung von 3-Isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanat (Isophorondiisocyanat = IPDI).Other organic polyisocyanates b) include aliphatic, cycloaliphatic and aromatic polyisocyanates. Suitable polyisocyanates b) are, for example, compounds of the formula Q (NCO) n having an average molecular weight below 800, where n is a number from 2 to 4 and Q is an aliphatic C 4 -C 12 -hydrocarbon radical or a cycloaliphatic C 6 -C 15 -hydrocarbon radical For example, diisocyanates from the series 4,4'-diisocyanatodicyclohexylmethane, 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate (Isophorone diisocyanate = IPDI), tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), 2-methylpentamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate (THDI), dodecamethylene diisocyanate, 1,4-diisocyanatocyclohexane, 4,4'-diisocyanato-3,3'- dimethyl-dicyclohexylmethane, 4,4'-diisocyanatodicyclohexylpropane (2,2), 3-isocyanatomethyl-1-methyl-1-isocyanatocyclohexane (IMCI), 1,3-diisooctylcyanato-4-methylcyclohexane, 1,3-diisocyanato 2-methyl-cyclohexane and α, α, α ', α'-tetramethyl-m- or -p-xylylen-diisocyanate (TMXDI) and mixtures consisting of these compounds. Furthermore, polyisocyanates, as described, for example, in "Methods of Organic Chemistry" (Houben-Weyl), Vol. 14/2, Georg Thieme Verlag, Stuttgart 1963, pages 61 to 70 and in Liebigs Annalen der Chemie 562, pages 75 to 136 may be used. Also aromatic polyisocyanates such as 2,4- and 2,6-toluene diisocyanate, their technical mixtures, or 2,4'- and 4,4'-diphenylmethane diisocyanates can be used, but are less preferred. However, the use of aliphatic diisocyanates is particularly preferred, and the use of 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate = IPDI) is particularly preferred.
Bevorzugte NCO-reaktive Verbindungen c) sind vor allem Polyole. Als Polyole können höhermolekulare und in untergeordneter Menge auch niedermolekulare Hydroxylverbindungen eingesetzt werden.Preferred NCO-reactive compounds c) are especially polyols. As polyols, it is possible to use relatively high molecular weight and, to a lesser extent, low molecular weight hydroxyl compounds.
Höhermolekulare Hydroxylverbindungen umfassen die in der Polyurethan-Chemie üblichen Hydroxypolyester, Hydroxypolyether, Hydroxypolythioether, Hydroxypolyacetale, Hydroxypolycarbonate, Dimerfettalkohole und/oder Esteramide, jeweils mit mittleren Molekulargewichten von 400 bis 8 000, bevorzugt solche mit mittleren Molekulargewichten von 500 bis 6 500. Es werden vorzugsweise nur Diole eingesetzt, da die Verzweigung üblicherweise über die Polyisocyanatkomponente a) oder b) eingebracht wird.Higher molecular weight hydroxyl compounds include the usual in polyurethane chemistry hydroxypolyesters, hydroxypolyethers, hydroxypolythioethers, hydroxypolyacetals, hydroxypolycarbonates, dimer fatty alcohols and / or ester amides, each having average molecular weights from 400 to 8,000, preferably those having average molecular weights from 500 to 6 500. It is preferably only diols are used since the branching is usually introduced via the polyisocyanate component a) or b).
Als niedermolekulare Polyhydroxylverbindungen können in der Polyurethan-Chemie übliche Polyole, mit Molekulargewichten von 62 bis 399, wie Ethylenglykol, Triethylenglykol, Tetraethylenglykol, Propandiol-1,2 und -1,3, Butandiol-1,4- und -1,3, Hexandiol-1,6, Octandiol-1,8, Neopentylglykol, 1,4-Bis(hydroxymethyl)cyclohexan, Bis(hydroxymethyl)tricyclo[5.2.1.02.6]decan oder 1,4-Bis(2-hydroxyethoxy)benzol, 2-Methyl-1,3-propandiol, 2,2,4-Trimethylpentandiol, 2-Ethyl-1,3-hexandiol, Dipropylenglykol, Polypropylenglykole, Dibutylenglykol, Polybutylenglykole, Bisphenol A, Tetrabrombisphenol A, Glycerin, Trimethylolpropan, Hexantriol-1,2,6-Butantriol-1,2,4, Pentaerythrit, Chinit, Mannit, Sorbit, Methylglykosid und 4,3,6-Dianhydrohexite verwendet werden.As low molecular weight polyhydroxyl compounds in polyurethane chemistry conventional polyols, with molecular weights of 62 to 399, such as ethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol and 1,3, 1,4-butanediol and 1,3, hexanediol 1,6, octanediol-1,8, neopentyl glycol, 1,4-bis (hydroxymethyl) cyclohexane, bis (hydroxymethyl) tricyclo [5.2.1.0 2.6] decane or 1,4-bis (2-hydroxyethoxy) benzene, 2- Methyl-1,3-propanediol, 2,2,4-trimethylpentanediol, 2-ethyl-1,3-hexanediol, dipropylene glycol, polypropylene glycols, dibutylene glycol, polybutylene glycols, bisphenol A, tetrabromobisphenol A, glycerol, trimethylolpropane, hexanetriol-1,2, 6-butanetriol-1,2,4, pentaerythritol, quinitol, mannitol, sorbitol, methyl glycoside and 4,3,6-dianhydrohexite.
Als Polyetherpolyole geeignet sind die in Polyurethan-Chemie üblichen Polyether, wie z.B. die unter Verwendung von zwei- bis sechswertigen Startermolekülen wie Wasser oder den oben genannten Polyolen oder 1- bis 4-NH-Bindungen aufweisenden Aminen hergestellten Additions- bzw. Mischadditionsverbindungen des Tetrahydrofurans, Styroloxids, Ethylenoxids, Propylenoxids, der Butylenoxide oder des Epichlorhydrins, insbesondere des Ethylenoxids und/oder des Propylenoxids.Suitable polyether polyols are the polyethers customary in polyurethane chemistry, e.g. the addition or Mischadditionsverbindungen of tetrahydrofuran, styrene oxide, ethylene oxide, propylene oxide, the butylene oxides or epichlorohydrin, in particular of the prepared using two- to hexavalent starter molecules such as water or the above-mentioned polyols or 1- to 4-NH bonds Ethylene oxide and / or propylene oxide.
Als Polyesterpolyole geeignet sind z.B. Umsetzungsprodukte von mehrwertigen, vorzugsweise zweiwertigen und gegebenenfalls zusätzlich dreiwertigen Alkoholen mit mehrbasischen, vorzugsweise zweibasischen Carbonsäuren. Anstelle der freien Polycarbonsäuren können auch die entsprechenden Polycarbonsäureanhydride oder entsprechende Polycarbonsäureester von niedrigen Alkoholen oder deren Gemische zur Herstellung der Polyester verwendet werden. Die Polycarbonsäuren können aliphatischer, cycloaliphatischer aromatischer und/oder heterocyclischer Natur sein und gegebenenfalls z.B. durch Halogenatome substituiert und/oder ungesättigt sein. Beispiele hierfür sind:Suitable polyester polyols are e.g. Reaction products of polyhydric, preferably dihydric and optionally additionally trihydric alcohols with polybasic, preferably dibasic carboxylic acids. Instead of the free polycarboxylic acids, it is also possible to use the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols or mixtures thereof to prepare the polyesters. The polycarboxylic acids may be aliphatic, cycloaliphatic, aromatic and / or heterocyclic in nature, and optionally, e.g. substituted by halogen atoms and / or unsaturated. Examples for this are:
Adipinsäure, Phthalsäure, Isophthalsäure, Bernsteinsäure, Korksäure, Azelainsäure, Sebacinsäure, Trimellitsäure, Phthalsäureanhydrid, Tetrahydrophthalsäureanhydrid, Glutarsäureanhydrid, Tetrachlorphthalsäureanhydrid, Endomethylentetrahydrophthalsäureanhydrid, Maleinsäureanhydrid, Maleinsäure, Fumarsäure, dimere und trimere Fettsäuren wie Ölsäure, gegebenenfalls in Mischung mit monomeren Fettsäuren, Terephthalsäuredimethylester, Terephthalsäure-bis-glykolester.Adipic, phthalic, isophthalic, succinic, suberic, azelaic, sebacic, trimellitic, phthalic, tetrahydrophthalic, glutaric, tetrachlorophthalic, endomethylenetetrahydrophthalic anhydride, Maleic anhydride, maleic acid, fumaric acid, dimeric and trimeric fatty acids such as oleic acid, optionally in admixture with monomeric fatty acids, terephthalic acid dimethyl ester, terephthalic acid bis-glycol ester.
Als mehrwertige Alkohole kommen die oben genannten Polyole in Frage.Suitable polyhydric alcohols are the abovementioned polyols.
Die in Frage kommenden Polycarbonatpolyole sind durch Reaktion von Kohlensäurederivaten, z.B. Diphenylcarbonat oder Phosgen, mit Diolen erhältlich. Als derartige Diole kommen z.B. Ethylenglykol, Triethylenglykol, Tetraethylenglykol, Propandiol-1,2 und -1,3,-Butandiol-1,4- und -1,3, Pentandiol-1,5, Hexandiol-1,6, Octandiol-1,8, Neopentylgkylol, 1,4-Bis(hydroxymethyl)cyclohexan, Bis(hydroxymethyl)tricyclo-[5.2.1.02.6]decan oder 1,4-Bis(2-hydroxyethoxy)benzol, 2-Methyl-1,3-propandiol, 2,2,4-Trimethylpentandiol, Dipropylenglykol, Polypropylenglykole, Dibutylenglykol, Polybutylenglykole, Bisphenol A und Tetrabrombisphenol A oder Mischungen der genannten Diole in Frage. Vorzugweise erhält die Diolkomponente 40 bis 100 Gew.-% Hexandiol, vorzugsweise Hexandiol-1,6, und/oder Hexandiol-Derivate, vorzugsweise solche, die neben endständigen OH-Gruppen Ether- oder Estergruppen aufweisen, z.B. Produkte, die durch Umsetzung von 1 Mol Hexandiol mit mindestens 1 Mol, bevorzugt 1 bis 2 Mol Caprolacton gemäß DE-A 1 770 245, oder durch Veretherung von Hexandiol mit sich selbst zum di- oder Trihexylenglykol erhalten wurden. Die Herstellung solcher Derivate ist z.B. aus DE-A 1 570 540 bekannt. Auch die in der DE-A 3 717 060 beschriebenen Polyether-Polycarbonatdiole können eingesetzt werden.The polycarbonate polyols in question are obtainable by reaction of carbonic acid derivatives, for example diphenyl carbonate or phosgene, with diols. Examples of such diols are ethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol and 1,3-butanediol-1,4-and 1,3-pentanediol-1,5-hexanediol-1,6-octanediol-1 , 8, Neopentylgkylol, 1,4-bis (hydroxymethyl) cyclohexane, bis (hydroxymethyl) tricyclo [5.2.1.0 2.6] decane or 1,4-bis (2-hydroxyethoxy) benzene, 2-methyl-1,3-propanediol , 2,2,4-trimethylpentanediol, dipropylene glycol, polypropylene glycols, dibutylene glycol, polybutylene glycols, bisphenol A and tetrabromobisphenol A or mixtures of said diols in question. Preferably, the diol component contains 40 to 100 wt .-% of hexanediol, preferably 1,6-hexanediol, and / or hexanediol derivatives, preferably those which in addition to terminal OH groups ether or ester groups, for example products which by reaction of 1 Mol hexanediol with at least 1 mole, preferably 1 to 2 moles of caprolactone according to DE-A 1 770 245, or by etherification of hexanediol with itself to di- or Trihexylenglykol were obtained. The preparation of such derivatives is known, for example, from DE-A 1 570 540. The polyether-polycarbonate diols described in DE-A 3 717 060 can also be used.
Die Hydroxypolycarbonate sollen im Wesentlichen linear sein. Sie können aber auch gegebenenfalls durch den Einbau polyfunktioneller Komponenten, insbesondere niedermolekularer Polyole, leicht verzweigt werden. Hierzu eignen sich beispielsweise Trimethylolpropan, Hexantriol-1,2,6, Glycerin, Butantriol-1,2,4, Pentaerythrit, Chinit, Mannit, Sorbit, Methylglykosid und 4,3,6-Dianhydrohexite.The hydroxypolycarbonates should be substantially linear. However, they can also be easily branched if appropriate by the incorporation of polyfunctional components, in particular low molecular weight polyols. Trimethylolpropane, hexanetriol-1,2,6, glycerol, butanetriol-1,2,4, pentaerythritol, quinitol, mannitol, sorbitol, methylglycoside and 4,3,6-dianhydrohexite are suitable for this purpose, for example.
Ganz besonders bevorzugt sind im Durchschnitt 2 bis 3 Hydroxylgruppen aufweisende Propylenoxidpolyether, die bis zu maximal 50 Gew.-% eingebaute Polyethylenoxid-Einheiten enthalten mit mittleren Molekulargewichten zwischen 200 und 9 000, und/oder difunktionelle Tetrahydrofuran-Polyether mit mittleren Molekulargewichten zwischen 200 und 4 000 und/oder Polypropylenoxydpolyether mit einem Gesamt-Unsättigungsgrad von maximal 0,04 mÄq/g und einem mittleren, aus OH-Gehalt und Funktionalität berechneten Molekulargewicht von 2 000 bis 12 000 eingesetzt.Very particular preference is given on average to 2 to 3 hydroxyl-containing propylene oxide polyethers containing up to a maximum of 50% by weight of incorporated polyethylene oxide units containing average molecular weights of between 200 and 9,000, and / or difunctional tetrahydrofuran polyethers having average molecular weights of between 200 and 4,000 and / or polypropylene oxide polyethers having a total unsaturation of not more than 0.04 meq / g and an average OH content and functionality calculated molecular weight of 2,000 to 12,000 used.
Die erfindungsgemäß besonders bevorzugt einsetzbaren Polyetherpolyole mit niedrigem Unsättigungsgrad sind prinzipiell bekannt und werden beispielhaft in der DE-A 1 984 817 (PCT/99/07883) und den darin zitierten Veröffentlichungen beschrieben. Schlüssel zur Herstellung derartiger Polyetherpolyole mit niedrigem Unsättigungsgrad ist die Katalyse mit Metallcyaniden.The polyether polyols having a low degree of unsaturation which are particularly preferably usable according to the invention are known in principle and are described by way of example in DE-A 1 984 817 (PCT / 99/07883) and the publications cited therein. Key to the preparation of such low unsaturation polyether polyols is catalysis with metal cyanides.
Die Herstellung der Komponente A) erfolgt vorzugsweise durch Umsetzung des Uretdion- und/oder Oxadiazintrion-haltigen Polyisocyanats a) mit den genannten Polyhydroxylverbindungen c) bei ca. 40 bis 100°C, wobei ein NCO/OH-Verhältnis von 1,5:1 bis 5:1, vorzugsweise 1,7:1 bis 4:1, eingestellt wird.The preparation of component A) is preferably carried out by reacting the uretdione and / or oxadiazinetrione-containing polyisocyanate a) with said polyhydroxyl c) at about 40 to 100 ° C, wherein an NCO / OH ratio of 1.5: 1 to 5: 1, preferably 1.7: 1 to 4: 1, is set.
Falls weitere Polyisocyanate b) eingesetzt werden, können diese, wenn es sich um difunktionelle Typen handelt, zur Vorverlängerung der Polyhydroxylverbindungen c) eingesetzt werden. Höherfunktionelle Typen werden vorzugsweise in Mischung mit a) eingesetzt oder nachträglich zugegeben. Die Komponente A) kann zwecks Einstellung der optimalen Verarbeitungsviskosität von 20 000 bis 40 000 mPas bei 20°C mit bis zu 30 Gew.-%, vorzugsweise bis 20 Gew.-%, bezogen auf das NCO-Prepolymerisat, an organischen Lösungsmitteln wie beispielsweise Methoxypropylacetat oder Butylacetat gemischt werden.If further polyisocyanates b) are used, these can, if they are difunctional types, be used to pre-extend the polyhydroxyl compounds c). Higher functional types are preferably used in admixture with a) or added subsequently. Component A) can, for the purpose of setting the optimum processing viscosity of from 20,000 to 40,000 mPas at 20 ° C with up to 30 wt .-%, preferably up to 20 wt .-%, based on the NCO prepolymer, of organic solvents such as Methoxypropylacetat or butyl acetate are mixed.
Die Komponente B) besteht vorzugsweise zu mehr als 80 Äquivalent-%, besonders bevorzugt zu 100 Äquivalent-%, bezogen auf die gegenüber Isocyanat reaktiven Gruppen, aus Verbindungen der Formel III. Bevorzugte Verbindungen III sind Verbindungen, die sich auch in Prepolymer A unter 50°C nicht lösen. Besonders bevorzugte Verbindungen III umfassen beispielsweise 1,2-Bis(2-hydroxyethoxy)benzol, 1-3-Bis(2-hydroxyethoxy)benzol, Bis-1,4-(hydroxymethyl)benzol, trans-1,4-Bis(hydroxymethyl)-cyclohexan, 1,2-Bis(4-hydroxycyclohexyl)ethan, Bis(4-hydroxycyclohexyl)methan, 2-Butin-1,4-diol, Die besonders bevorzugte Verbindung III ist 1,4-Bis-(2-hydroxyethoxy)-benzol.Component B) is preferably more than 80 equivalent%, more preferably 100 equivalent%, based on the isocyanate-reactive groups, of compounds of formula III. Preferred compounds III are compounds which do not dissolve in prepolymer A below 50 ° C. Particularly preferred compounds III include, for example, 1,2-bis (2-hydroxyethoxy) benzene, 1-3-bis (2-hydroxyethoxy) benzene, Bis-1,4- (hydroxymethyl) benzene, trans-1,4-bis (hydroxymethyl) cyclohexane, 1,2-bis (4-hydroxycyclohexyl) ethane, bis (4-hydroxycyclohexyl) methane, 2-butyne-1, 4-diol, The most preferred compound III is 1,4-bis (2-hydroxyethoxy) benzene.
Die Komponente B) kann als solche zur Herstellung der Reaktivbindemittel direkt mit dem Prepolymer gemischt werden. Es hat sich aber zwecks besserer Dosierbarkeit als günstig erwiesen, die normalerweise festen Verbindungen III in einer flüssigen Komponente anzurühren. Solche Mischungen bestehen dann vorzugsweise aus 20 bis 90, besonders bevorzugt 30 bis 70 Gew.% Verbindungen III und 10 bis 80, besonders bevorzugt 30 bis 70 Gew.-% flüssige Komponente sowie 0 bis 10 Gew-%, vorzugsweise 0,1 bis 5 Gew.-% weiterer Zusatzstoffe wie Dispergiermittel, Antiabsetzmittel, Katalysatoren usw. Die flüssige Komponente kann eines der oben beschriebenen höhermolekularen Polyole und/oder ein nicht mit Isocyanaten reagierender Weichmacher und/oder ein beliebiges Lösungsmittel sein. Beispiele für geeignete Solventien sind die üblichen Lacklösemittel: Ester wie Butylacetat, Etherester wie Methoxypropylacetat, Ketone wie Aceton und 2-Butanon, Aromaten wie Xylol, Toluol oder technische Aromaten- oder Aliphatengemische oder auch dipolare Solventien wie beispielsweise N-Methylpyrrolidon, N,N-Dimethylacetamid, N,N-Dimethylformamid und Dimethylsulfoxid oder Mischungen verschiedener Lösungsmittel.Component B) can be mixed as such to prepare the reactive binder directly with the prepolymer. However, it has proved to be favorable for better dosing to touch the normally solid compounds III in a liquid component. Such mixtures then preferably consist of 20 to 90, more preferably 30 to 70 wt.% Compounds III and 10 to 80, particularly preferably 30 to 70 wt .-% liquid component and 0 to 10 wt%, preferably 0.1 to 5 % By weight of further additives such as dispersants, anti-settling agents, catalysts, etc. The liquid component may be one of the above-described higher molecular weight polyols and / or a non-isocyanate-reactive plasticizer and / or any desired solvent. Examples of suitable solvents are the conventional lacquer solvents: esters such as butyl acetate, ether esters such as methoxypropyl acetate, ketones such as acetone and 2-butanone, aromatics such as xylene, toluene or technical aromatic or aliphatic mixtures or else dipolar solvents such as N-methylpyrrolidone, N, N- Dimethylacetamide, N, N-dimethylformamide and dimethyl sulfoxide or mixtures of various solvents.
Als flüssige Komponente sind Lösungsmittel bevorzugt. Besonders bevorzugt sind toxikologisch weniger kritische aliphatische Ester oder Etherester wie beispielsweise Methoxypropylacetat oder Butylacetat.As the liquid component, solvents are preferred. Particularly preferred are less toxic aliphatic esters or ether esters such as methoxypropyl acetate or butyl acetate.
Um eine gute Oberflächenstruktur des Films zu gewährleisten, hat es sich als zweckmäßig erwiesen, dass die feste Verbindung III in feiner Verteilung vorliegt. Die bevorzugte Größenverteilung der Teilchen liegt bei d90 = 1 bis 80 µm und d99 = 5 bis 120 µm, bevorzugt d90 = 3 bis 40 µm und d99 = 5 bis 60 µm. Die Verbindung III wird dann üblicherweise mit einem Dissolver in die flüssige Komponente eingearbeitet. Es ist aber auch möglich, eine übersättigter Lösung der Verbindung III durch Rekristallisieren in die gewünschte Dispersion zu überführen oder die Verbindung III aus der Schmelze zu dispergieren. Eine Herstellung in den in der Lackindustrie üblichen Perlmühlen ist ebenfalls möglich.In order to ensure a good surface structure of the film, it has proven expedient that the solid compound III is in fine distribution. The preferred size distribution of the particles is d90 = 1 to 80 μm and d99 = 5 to 120 μm, preferably d90 = 3 to 40 μm and d99 = 5 to 60 μm. The compound III is then usually incorporated with a dissolver in the liquid component. But it is also possible, a supersaturated solution of compound III by recrystallization into the desired dispersion or to disperse the compound III from the melt. A production in the usual in the paint industry bead mills is also possible.
Die rheologischen Eigenschaften und das Absetzverhalten kann durch spezielle Additive wie hydrierte Ricinusöle, Polyharnstoffderivate oder spezielle Kieselsäuren günstig beeinflußt werden (siehe J. Beilman, "Lackadditive", Wiley-VCH-Verlag GmbH. 1998). Als Dispergiermittel sind insbesondere polymere Additive geeignet. Sie bestehen vorzugsweise aus chemisch unterschiedlichen Segmenten, die je nach Struktur entweder mit der Oberfläche der zu dispergierenden Teilchen in Wechselwirkung treten oder aber als solvatisierte Ketten zu deren sterischer Stabilisierung beitragen. Als Beispiele der funktionellen Gruppen, die mit den Pigment- oder Füllstoffteilchen oder aber mit der kristallinen Verbindung III in der erfindungsgemäßen Vernetzerkomponente B in Wechselwirkung treten können, sind Carbonyl-, Amino-, Sulfat- oder Phosphatgruppen zu nennen. Beispiele für Polymersegmente, die zur Stabilisierung der Teilchen beitragen, sind Polyether, Polyester oder Polyacrylate.The rheological properties and the settling behavior can be favorably influenced by special additives such as hydrogenated castor oils, polyurea derivatives or special silicic acids (see J. Beilman, "Lackadditive", Wiley-VCH-Verlag GmbH, 1998). As dispersants in particular polymeric additives are suitable. They preferably consist of chemically different segments which, depending on the structure, either interact with the surface of the particles to be dispersed or, as solvated chains, contribute to their steric stabilization. Examples of the functional groups which may interact with the pigment or filler particles or with the crystalline compound III in the crosslinker component B according to the invention are carbonyl, amino, sulfate or phosphate groups. Examples of polymer segments which contribute to the stabilization of the particles are polyethers, polyesters or polyacrylates.
Die crfindungsgemäße Einsatzmenge der Katalysatoren, die als Bestandteil der Komponente B oder als Katalysatorlösung in einem beliebigen Lösungsmittel eingesetzt werden kann beträgt 0,001 bis 2, bevorzugt 0,005 bis 0,5 Gew.-%, bezogen auf das Gesamtgewicht der Komponente A + Komponente B. Ganz besonders geeignet im Sinne der Erfindung sind Dioctylzinn-IV-bis(2-ethylhexylmercaptoacetat), Dibutylzinn-IV-bis(2-ethylhexylmercaptoacetat) und Dimethylzinn-IV-bis(2-ethylhexylmercaptoacetat) sowie latente Katalysatoren aus Zinn- oder Wismutverbindungen und Mercaptoverbindungen, wie sie z.B. in der US-A 4 788 083 beschrieben sind.The amount of catalysts according to the invention which can be used as constituent of component B or as catalyst solution in any solvent is 0.001 to 2, preferably 0.005 to 0.5,% by weight, based on the total weight of component A + component B. Ganz Particularly suitable for the purposes of the invention are dioctyltin-IV-bis (2-ethylhexylmercaptoacetate), dibutyltin-IV-bis (2-ethylhexylmercaptoacetate) and dimethyltin-IV-bis (2-ethylhexylmercaptoacetate) and also latent catalysts of tin or bismuth compounds and mercapto compounds, as they eg in US Pat. No. 4,788,083.
Die Vermischung des NCO-Prepolymerisats A mit der Kettenverlängererkomponente B erfolgt im allgemeinen etwa im Verhältnis der Äquivalentgewichte dieser Komponenten, obwohl für einige Anwendungszwecke auch eine Untervemetzung zweckmäßig ist, so dass das Äquivalentverhältnis von NCO zu OH erfindungsgemäß im Allgemeinen 0,90 bis 1,50, bevorzugt 1,0 bis 1,3 beträgt.The mixing of the NCO prepolymer A with the chain extender component B is generally about in the ratio of the equivalent weights of these components, although for some applications, a sub-crosslinking is appropriate, so that the equivalent ratio of NCO to OH according to the invention generally 0.90 to 1.50 , preferably 1.0 to 1.3.
Zur Herstellung der gebrauchtsfertigen Reaktivmassen können Zuschläge wie z.B. Pigmente, UV-Stabilisatoren, Verlaufmittel, Antioxidantien, Füllstoffe oder Treibmittel beigemischt werden.To prepare the ready-to-use reactive compositions, additives such as e.g. Pigments, UV stabilizers, flow control agents, antioxidants, fillers or blowing agents.
Es können Lackhilfsmittel eingesetzt werden, wie sie beispielsweise in J. Beilman, "Lackadditive", Wiley-VCH-Verlag GmbH, 1998 beschrieben sind. Insbesondere sind Verlauf und Dispergiermittel sowie rheologische Additive für die Herstellung der erfindungsgemäßen Massen geeignet. So können beispielsweise Additive auf Siliconbasis zur Verbesserung der Oberflächeneigenschaften eingesetzt werden. Zur Verbesserung des Verlaufs eignen sich besonders Additive auf Basis von Polyacrylaten. Die rheologischen Eigenschaften der Massen und das Absetzverhalten füllstoff- und pigmenthaltiger Massen kann durch spezielle Additive wie hydrierte Ricinusöle, Polyharnstoffderivate oder spezielle Kieselsäuren günstig beeinflußt werden.Paint assistants can be used, as described, for example, in J. Beilman, "Lackadditive", Wiley-VCH-Verlag GmbH, 1998. In particular, flow and dispersants and rheological additives are suitable for the preparation of the compositions of the invention. For example, silicone-based additives can be used to improve surface properties. To improve the course are particularly suitable additives based on polyacrylates. The rheological properties of the compositions and the settling behavior of fillers and pigment-containing compositions can be favorably influenced by special additives such as hydrogenated castor oils, polyurea derivatives or special silicas.
Lackadditive, die den erfindungsgemäßen Massen beigesetzt werden können, können in Mengen von 0,01 bis 5 Gew.-%, vorzugsweise 0,05 bis 3 Gew.%, eingesetzt werden.Lacquer additives which can be added to the compositions of the invention can be used in amounts of from 0.01 to 5% by weight, preferably from 0.05 to 3% by weight.
Weiterhin können den erfindungsgemäßen Massen flammhemmende Zusätze beigemischt werden. Darunter sind feste oder flüssige Stoffe zu verstehen, deren Zusatz eine Verbesserung des Brandverhaltens des ausgehärteten Polymerfilms bewirkt. Diese Mittel sind z.B. in Journal of Coated Fabrics 1996, Vol. 25, 224 ff beschrieben. Besonders geeignet für die Anwendung in den erfindungsgemäßen Massen sind halogen- und antimonfieie Flammschutzmittel wie Phosphor- oder Borsäurederivate, Calciumcarbonat, Aluminiumhydroxid, Magnesiumhydroxid oder Melamin und Melaminderivate. Besonders bevorzugt ist Melamin und seine Derivate wie beispielsweise Melaminborat oder Melaminisocyanurat. Die Flammschutzmittel können den erfindungsgemäßen Massen zu 2 bis 70 Gew.-%, bevorzugt 5 bis 35 Gew.-%, bezogen auf die Summe der Komponente A + B, zugegeben werden.Furthermore, flame-retardant additives can be added to the compositions of the invention. These are solid or liquid substances whose addition causes an improvement in the fire behavior of the cured polymer film. These agents are described, for example, in Journal of Coated Fabrics 1996, Vol. 25, 224 et seq. Particularly suitable for use in the compositions of the invention are halogen and Antimonfieie flame retardants such as phosphoric or boric acid derivatives, calcium carbonate, aluminum hydroxide, magnesium hydroxide or melamine and melamine derivatives. Particularly preferred is melamine and its derivatives such as melamine borate or melamine isocyanurate. The flame retardants may be added to the compositions of the invention to 2 to 70 wt .-%, preferably 5 to 35 wt .-%, based on the sum of the component A + B.
Die erfindungsgemäßen reaktionsfähigen Massen werden vorzugsweise durch Rakeln (Streichen) nach dem Direkt- oder Umkehrbeschichtungsverfahren verarbeitet.The reactive compositions according to the invention are preferably processed by doctoring (brushing) by the direct or reverse coating method.
Die Aushärtungszeit der erfindungsgemäßen Massen beträgt 2 bis 18, vorzugsweise 6 bis 12 Minuten. Die kurze Aushärtungszeit ermöglicht es, mit hoher Geschwindigkeit zu beschichten. Natürlich ist es möglich, durch einen jeweiligen spezifischen chemischen Aufbau des NCO-Prepolymerisates Schichten mit unterschiedlichen Eigenschaften, wie z.B. eine Haft-, Schaum-, Zwischen- oder Deckschicht, zu erzeugen.The curing time of the compositions according to the invention is 2 to 18, preferably 6 to 12 minutes. The short curing time makes it possible to coat at high speed. Of course, it is possible by a respective specific chemical structure of the NCO prepolymer layers with different properties, such as. an adhesive, foam, intermediate or cover layer to produce.
Die Herstellung z.B. einer Umkehrbeschichtung kann beispielsweise folgendermaßen erfolgen: Man trägt zuerst auf einen geeigneten Zwischenträger, z.B. ein Trennpapier, die Reaktivmasse für den Deckstrich in einer Menge von ca. 30 bis 100 g/m2 auf, härtet im Trockenkanal aus, bringt auf den trockenen Deckstrich die Reaktivmasse für den Haftstrich ebenfalls in einer Menge von ca. 30 bis 100 g/m2, kaschiert das Substrat hinzu, härtet die Beschichtung in einem weiteren Trockenkanal bei ca. 120 bis 190°C, vorzugsweise 140 bis 170°C, aus und zieht das beschichtete Substrat vom Trennträger ab. Selbstverständlich ist es auch möglich, nur den Deck-, Zwischen- oder Haftstrich nach diesem Beschichtungsverfahren zu erzeugen und für den anderen Strich andere Beschichtungssysteme des Standes der Technik einzusetzen.The preparation of, for example, a reverse coating may for example be done as follows: It is first applied to a suitable intermediate support, eg a release paper, the reactive composition for the top coat in an amount of about 30 to 100 g / m 2, cured in a drying tunnel, brings to the dry top coat, the reactive composition for the adhesive coat also in an amount of about 30 to 100 g / m 2, laminated thereto, the substrate, the coating is cured in another drying tunnel at about 120 to 190 ° C, preferably 140 to 170 ° C, and withdraws the coated substrate from the release liner. Of course, it is also possible to produce only the cover, intermediate or adhesive coat after this coating process and to use other coating systems of the prior art for the other stroke.
Wie schon erwähnt, können die Reaktivmassen aber auch im Direktstreichverfahren unmittelbar auf das textile Substrat aufgebracht werden. Hierbei ist der abspalterfreie und lösungsmittelarme Charakter der erfindungsgemäßen Reaktivmassen von großem Vorteil bei der Herstellung von dicken Planenbeschichtungen. Mit Auftragsmengen von 100 bis 200 g/m2 können auf diese Weise ca. 0,4 mm dicke, technische Beschichtungen in nur einem Arbeitsgang erstellt werden.As already mentioned, however, the reactive compositions can also be applied directly to the textile substrate in a direct coating process. Here, the splitter-free and low-solvent character of the reactive compositions of the invention is of great advantage in the production of thick tarpaulin coatings. With application quantities of 100 to 200 g / m 2 , about 0.4 mm thick, technical coatings can be created in this way in only one operation.
Sollen mit den erfindungsgemäßen Reaktivmassen Schaumschichten hergestellt werden, dann setzt man ihnen Treibmittel sowie zweckmäßigerweise auch Schaumstabilisatoren zu. Geeignete Zusätze werden z.B. in der DE-A 1 794 006 sowie in der US-A 3 262 805 beschrieben.If foam layers are to be produced with the reactive compositions according to the invention, then they are added to blowing agents and, expediently, to foam stabilizers. Suitable additives are described, for example, in DE-A 1 794 006 and in US Pat. No. 3,262,805.
2000 g (2 Äquiv) Polytetrahydrofuran mit einem mittleren Molekulargewicht von 2000 (Terathane® 2000, DuPont) wird zunächst bei 100°C mit 111 g (1 Äquiv) Isophorondiisocyanat bis zum Verschwinden der Isocyanatbande im IR-Spektrum umgesetzt. Anschließend werden 671 g Methoxypropylacetat zugesetzt und auf 40°C abgekühlt.2000 g (2 equiv) of polytetrahydrofuran having an average molecular weight of 2000 (Terathane® 2000, DuPont) is first reacted at 100 ° C. with 111 g (1 equiv) of isophorone diisocyanate until the disappearance of the isocyanate band in the IR spectrum. Then 671 g of methoxypropyl acetate are added and cooled to 40 ° C.
Man gibt in einem Guß 193 g (1 Äquiv) Desmodur® N 3400 (Bayer AG, DE) und 380 g (2 Äquiv) 3,5-Bis-[6-isocyanatohexyl]-1,3,5-oxadiazin-2,4,6-trion (hergestellt nach DE-A 1 670 666) zu und erhitzt auf 75°C bis ein NCO-Gehalt von 2,4 % erreicht ist. Das Prepolymer hat einen Festkörpergehalt von 80 % eine Viskosität von 35 000 mPas bei 23°C und ein Isocyanat-Äquivalentgewicht von 1 750 g.193 g (1 equiv) of Desmodur® N 3400 (Bayer AG, DE) and 380 g (2 equiv) of 3,5-bis- [6-isocyanatohexyl] -1,3,5-oxadiazine-2 are added in one casting. 4,6-trione (prepared according to DE-A 1 670 666) and heated to 75 ° C until an NCO content of 2.4% is reached. The prepolymer has a solids content of 80%, a viscosity of 35,000 mPas at 23 ° C and an isocyanate equivalent weight of 1 750 g.
2 000 g (2 Äquiv) Desmophen® C200 (lineares Polyestercarbonatdiol mit mittlerem Molgewicht 2 000; Bayer AG, DE) wird zunächst bei 100°C mit 111 g (1 Äquiv) Isophorondiisocyanat und 150 g Methoxypropylacetat bis zum Verschwinden der Isocyanatbande im IR-Spektrum umgesetzt. Anschließend werden weitere 571 g Methoxypropylacetat zugesetzt und auf 40°C abgekühlt. Man gibt in einem Guß 772 g (4 Äquiv) Desmodur® N 3400 (Bayer AG, DE) zu und erhitzt auf 75°C bis ein NCO-Gehalt von 3,1 % erreicht ist. Das Prepolymer hat einen Festkörpergehalt von 80 % und ein Isocyanat-Äquivalentgewicht von 1 355 g.2,000 g (2 equiv) of Desmophen® C200 (linear polyester carbonate diol of average molecular weight 2,000, Bayer AG, DE) is initially heated at 100 ° C. with 111 g (1 equiv) of isophorone diisocyanate and 150 g of methoxypropyl acetate until the disappearance of the isocyanate band in the IR. Spectrum implemented. Subsequently, a further 571 g of methoxypropyl acetate are added and cooled to 40 ° C. 772 g (4 equiv) of Desmodur® N 3400 (Bayer AG, DE) are added in one pour and heated to 75 ° C. until an NCO content of 3.1% is reached. The prepolymer has a solids content of 80% and an isocyanate equivalent weight of 1 355 g.
2 000 g (2 Äquiv) Polytetrahydrofuran mit einem mittleren Molekulargewicht von 2 000 (Terathane® 2000, DuPont) wird zunächst bei 100°C mit 111 g (1 Äquiv) Isophorondiisocyanat bis zum Verschwinden der Isocyanatbande im IR-Spektrum umgesetzt. Anschließend werden 683 g Methoxypropylacetat zugesetzt und auf 40°C abgekühlt. Man gibt in einem Guß 579 g (3 Äquiv) Desmodur® N 3400 (Bayer AG, DE) zu und erhitzt auf 75°C bis ein NCO-Gehalt von 2,4 % erreicht ist. Das Prepolymer hat einen Festkörpergehalt von 80 % und ein Isocyanat-Äquivalentgewicht von 1 750 g.2,000 g (2 equiv.) Of polytetrahydrofuran having an average molecular weight of 2,000 (Terathane® 2000, DuPont) is initially mixed at 100 ° C. with 111 g (1 equiv) of isophorone diisocyanate until the disappearance of the isocyanate band in the IR spectrum implemented. Subsequently, 683 g of methoxypropyl acetate are added and cooled to 40 ° C. 579 g (3 equiv.) Desmodur.RTM. N 3400 (Bayer AG, DE) are added in one pour and the mixture is heated to 75.degree. C. until an NCO content of 2.4% is reached. The prepolymer has a solids content of 80% and an isocyanate equivalent weight of 1 750 g.
40 g 1,4-Bis-(2-hydroxyethoxy)benzol mit einer Teilchengrößenverteilung d90 von 15 µm und d99 von 31 µm werden in einem Dissolver bei maximal 30°C in eine Lösung von 0,4 g Dibutylzinndilaurat und 0,4 g Thioglykolsäure-2-ethylhexylester in 60 g Methoxypropylacetat eingetragen. Die erhaltene Dispersion hat einen OH-Gehalt von 6,9 % und somit ein Äquivalentgewicht von 248 g.40 g of 1,4-bis (2-hydroxyethoxy) benzene having a particle size distribution d90 of 15 μm and d99 of 31 μm are dissolved in a dissolver at a maximum of 30 ° C. in a solution of 0.4 g of dibutyltin dilaurate and 0.4 g of thioglycolic acid 2-ethylhexyl ester in 60 g of methoxypropyl acetate registered. The dispersion obtained has an OH content of 6.9% and thus an equivalent weight of 248 g.
100 g des Prepolymerisats A1 werden mit 14,2 g der Komponente B, 1 g des Verlaufsmittels Levacast® Fluid SN (Bayer AG, DE) sowie 0,5 g Irganox® 1010 (Ciba Specialties) vermischt. Die Mischung hat eine Anfangsviskosität von etwa 29000 mPas, gemessen bei 23°C. Nach dem Auftrag auf ein Trennpapier in einer Schichtdicke von ca. 100 µm wird die Mischung durch stufenweise Hitzebehandlung (3 Min. 120°C und 3 Min 150°C) ausgehärtet. Man erhält einen elastischen, homogenen Film mit folgenden mechanischen Eigenschaften:
100 g des Prepolymerisats A2 werden mit 18,3 g der Komponente B, 1 g des Verlaufsmittels Levacast® Fluid SN (Bayer AG, DE) sowie 0,5 g Irganox® 1010 (Ciba Specialties) vermischt. Die Mischung hat eine Anfangsviskosität von etwa 40 000 mPas, gemessen bei 23°C. Nach dem Auftrag auf ein Trennpapier in einer Schichtdicke von ca. 100 µm wird die Mischung durch stufenweise Hitzebehandlung (3 Min. 120°C und 3 Min 150°C) ausgehärtet. Man erhält einen elastischen, homogenen Film mit folgenden mechanischen Eigenschaften:
100 g des Prepolymerisats A 1 werden mit 14,2 g der Komponente B, 1 g des Verlaufsmittels Levacast® Fluid SN (Bayer AG, DE) sowie 0,5 g Irganox® 1010 (Ciba Specialties) vermischt. Die Mischung hat eine Anfangsviskosität von etwa 45 000 mPas, gemessen bei 23°C. Nach dem Auftrag auf ein Trennpapier in einer Schichtdicke von ca. 100 µm wird die Mischung durch stufenweise Hitzebehandlung (3 Min. 120°C und 3 Min. 150°C) ausgehärtet. Man erhält einen elastischen, homogenen Film mit folgenden mechanischen Eigenschaften:
Claims (9)
- Polyurethane coatings which may be obtained by reaction of aliphatic, isocyanate-containing prepolymers A) with a polyol component B), wherein
the prepolymers A)
based on solids, contain 1-8 wt.% of NCO, have a free monomeric diisocyanate content of less than 2% and contain from 0.1 to 1.5 mole of aliphatically bound uretidione (I) and/or oxadiazine trione groups (II) per 1000 g of prepolymer
is composed of at least 50 equivalent %, based on the groups which are reactive towards isocyanate, of compounds corresponding to the formula
HO-X-Y-X-OH (III)
whereinY means methylene, ethylene, -C≡C-, cyclohexylene-1,4, -1,3, -1,2, phenylene-1,4, -1,3, -1,2 andX means methylene, -OCH2CH2- (the oxygen being bound to the Y), cyclohexylene-1,4, -1,3, -1,2,and
wherein the equivalent ratio of the free NCO groups of A to the NCO-reactive groups of B is 0.90 to 1.50. - Polyurethane coatings according to claim 1, characterised in that the polyol component is composed of at least 80 equivalent %, based on the groups which are reactive towards isocyanate, of 1,4-bis(2-hydroxyethoxy)benzene.
- Polyurethane coatings according to claims 1 or 2, characterised in that the prepolymer A) has a monomeric diisocyanate content of less than 0.5 wt.%.
- Polyurethane coatings according to any of claims 1 to 3, characterised in that polyisocyanates containing uretidione groups and oxadiazine trione groups based on hexamethylene diisocyanate are used, the molar ratio of oxadiazine trione groups to uretidione groups being 2.0 to 4.0.
- Use of the polyurethane coatings according to any of claims 1 to 4 for coating textile.
- Textile coated with the polyurethane coatings according to any of claims 1 to 4.
- Process for coating textile or leather, characterised in that a mixture of the substances used for the preparation of the polyurethane coatings according to any of claims 1 to 4 is applied to textile or leather by knife coating and allowed to react there.
- Process for coating textile or leather, characterised in that a mixture of the substances used for the preparation of the polyurethane coatings according to any of claims 1 to 4 is applied to textile or leather by casting and allowed to react there.
- Leather coated with the polyurethane coatings according to any of claims 1 to 4.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10009407A DE10009407A1 (en) | 2000-02-28 | 2000-02-28 | Polyurethane coatings, especially for textiles and leather, obtainable by reacting an aliphatic isocyanate prepolymer containing uretdione and/or oxadiazinetrione groups with a polyol component |
DE10009407 | 2000-02-28 | ||
PCT/EP2001/001654 WO2001064767A1 (en) | 2000-02-28 | 2001-02-15 | Polyurethane coatings, based on polyisocyanates containing uretdione and/or oxadiazinetrione groups |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1276785A1 EP1276785A1 (en) | 2003-01-22 |
EP1276785B1 true EP1276785B1 (en) | 2006-04-12 |
Family
ID=7632745
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP01955100A Expired - Lifetime EP1276785B1 (en) | 2000-02-28 | 2001-02-15 | Polyurethane coatings, based on polyisocyanates containing uretdione and/or oxadiazinetrione groups |
Country Status (18)
Country | Link |
---|---|
US (1) | US6806340B2 (en) |
EP (1) | EP1276785B1 (en) |
JP (1) | JP2003525326A (en) |
KR (1) | KR100655840B1 (en) |
CN (1) | CN1193054C (en) |
AT (1) | ATE323115T1 (en) |
AU (1) | AU2001272088A1 (en) |
BR (1) | BR0108722B1 (en) |
CA (1) | CA2401215C (en) |
CZ (1) | CZ296480B6 (en) |
DE (2) | DE10009407A1 (en) |
ES (1) | ES2261444T3 (en) |
HK (1) | HK1051698A1 (en) |
HU (1) | HUP0204527A3 (en) |
IL (2) | IL151298A0 (en) |
MX (1) | MXPA02008417A (en) |
PL (1) | PL357669A1 (en) |
WO (1) | WO2001064767A1 (en) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPWO2002077054A1 (en) * | 2001-03-21 | 2004-07-15 | 三井化学株式会社 | End-capped isocyanate prepolymer having oxadiazine ring, method for producing the same, and composition for surface coating material |
ATE537953T1 (en) * | 2002-12-27 | 2012-01-15 | Kahei Co Ltd | POLYURETHANE FOAM INSERT AND PRODUCTION METHOD FOR LAYER INSERT THEREFROM |
JP3776428B2 (en) | 2002-12-27 | 2006-05-17 | 株式会社加平 | Polyurethane foam sheet and method for producing laminate sheet using the same |
DE102004057699A1 (en) * | 2004-11-30 | 2006-06-01 | Henkel Kgaa | Two component-polyurethane adhesive (obtained by coating two adhesion compound with cathodic electrode lacquer coated steel sheets and exhibiting a dynamic impact wedge) comprises a polyol component and a polyisocyanate component |
CN101805559A (en) * | 2010-04-07 | 2010-08-18 | 杭州东科建筑节能材料有限公司 | Polyurethane paint |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS493000B1 (en) * | 1970-12-28 | 1974-01-23 | ||
US3998794A (en) * | 1972-04-29 | 1976-12-21 | Bayer Aktiengesellschaft | Polyurethane polyureas which contain uretdione groups |
DE2902090A1 (en) * | 1979-01-19 | 1980-07-24 | Bayer Ag | HEAT-CURABLE COATING MEASURES AND METHOD FOR COATING SUBSTRATES |
JPS5896658A (en) * | 1981-12-04 | 1983-06-08 | Takeda Chem Ind Ltd | One-pack thermosetting polyurethane coating composition |
JPS5898375A (en) * | 1981-12-08 | 1983-06-11 | Takeda Chem Ind Ltd | Composition for one-pack pressure-sensitive adhesive |
JPS58101175A (en) * | 1981-12-10 | 1983-06-16 | Takeda Chem Ind Ltd | Composition for two-pack pressure-sensitive adhesive |
US4522975A (en) * | 1984-06-01 | 1985-06-11 | Olin Corporation | Select NCO-terminated, uretdione group-containing polyurethane prepolymers and lignocellulosic composite materials prepared therefrom |
DE3643458A1 (en) * | 1986-12-19 | 1988-06-23 | Agfa Gevaert Ag | METHOD FOR PRODUCING A MAGNETIC RECORDING CARRIER |
DE4039194A1 (en) | 1990-12-08 | 1992-06-11 | Bayer Ag | METHOD FOR PRODUCING POLYURETHANE COATINGS |
DE19603245A1 (en) | 1996-01-30 | 1997-07-31 | Bayer Ag | Thin-film distillation of uretdione diisocyanates |
DE19632925A1 (en) | 1996-08-16 | 1998-02-19 | Bayer Ag | Responsive masses with a long pot life |
JPWO2002077054A1 (en) * | 2001-03-21 | 2004-07-15 | 三井化学株式会社 | End-capped isocyanate prepolymer having oxadiazine ring, method for producing the same, and composition for surface coating material |
-
2000
- 2000-02-28 DE DE10009407A patent/DE10009407A1/en not_active Withdrawn
-
2001
- 2001-02-15 JP JP2001564259A patent/JP2003525326A/en not_active Withdrawn
- 2001-02-15 AU AU2001272088A patent/AU2001272088A1/en not_active Abandoned
- 2001-02-15 MX MXPA02008417A patent/MXPA02008417A/en active IP Right Grant
- 2001-02-15 US US10/204,978 patent/US6806340B2/en not_active Expired - Fee Related
- 2001-02-15 CZ CZ20022919A patent/CZ296480B6/en not_active IP Right Cessation
- 2001-02-15 DE DE50109498T patent/DE50109498D1/en not_active Expired - Lifetime
- 2001-02-15 CN CNB018056636A patent/CN1193054C/en not_active Expired - Fee Related
- 2001-02-15 CA CA002401215A patent/CA2401215C/en not_active Expired - Fee Related
- 2001-02-15 KR KR1020027011204A patent/KR100655840B1/en not_active IP Right Cessation
- 2001-02-15 AT AT01955100T patent/ATE323115T1/en not_active IP Right Cessation
- 2001-02-15 IL IL15129801A patent/IL151298A0/en active IP Right Grant
- 2001-02-15 BR BRPI0108722-3A patent/BR0108722B1/en not_active IP Right Cessation
- 2001-02-15 PL PL01357669A patent/PL357669A1/en unknown
- 2001-02-15 WO PCT/EP2001/001654 patent/WO2001064767A1/en active IP Right Grant
- 2001-02-15 ES ES01955100T patent/ES2261444T3/en not_active Expired - Lifetime
- 2001-02-15 EP EP01955100A patent/EP1276785B1/en not_active Expired - Lifetime
- 2001-02-15 HU HU0204527A patent/HUP0204527A3/en unknown
-
2002
- 2002-08-15 IL IL151298A patent/IL151298A/en not_active IP Right Cessation
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2003
- 2003-06-05 HK HK03103969A patent/HK1051698A1/en not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
EP1276785A1 (en) | 2003-01-22 |
ATE323115T1 (en) | 2006-04-15 |
KR20020076339A (en) | 2002-10-09 |
CN1406257A (en) | 2003-03-26 |
CN1193054C (en) | 2005-03-16 |
AU2001272088A1 (en) | 2001-09-12 |
DE50109498D1 (en) | 2006-05-24 |
IL151298A (en) | 2007-02-11 |
KR100655840B1 (en) | 2006-12-12 |
US20030032756A1 (en) | 2003-02-13 |
BR0108722A (en) | 2002-11-26 |
BR0108722B1 (en) | 2011-06-14 |
MXPA02008417A (en) | 2003-02-12 |
HK1051698A1 (en) | 2003-08-15 |
HUP0204527A2 (en) | 2003-04-28 |
PL357669A1 (en) | 2004-07-26 |
CA2401215C (en) | 2008-10-14 |
US6806340B2 (en) | 2004-10-19 |
DE10009407A1 (en) | 2001-08-30 |
CZ296480B6 (en) | 2006-03-15 |
WO2001064767A1 (en) | 2001-09-07 |
CA2401215A1 (en) | 2001-09-07 |
HUP0204527A3 (en) | 2005-07-28 |
IL151298A0 (en) | 2003-04-10 |
JP2003525326A (en) | 2003-08-26 |
ES2261444T3 (en) | 2006-11-16 |
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